JP6641284B2 - Liquid-repellent resin sheet, molded article, and method for producing liquid-repellent resin sheet - Google Patents

Description

  The present invention relates to a resin sheet having liquid repellency and a molded product obtained by heating and stretching the resin sheet.

  Conventionally, as a sheet for building materials such as wallpaper, a sheet for packaging of soft drinks and fruit juice beverages, foods and daily necessities such as favorite foods and drinks, a sheet coated with a polymer material on a paper material has been used. . For example, Patent Document 1 proposes a sheet in which a nonwoven fabric is coated with a fluorine-based copolymer. Patent Documents 2 and 3 also propose liquid repellents for paper materials and cloths.

  On the other hand, for display members and the like, a film in which a PET resin is coated with an oil repellent has been proposed (Patent Document 4). Furthermore, as for automotive parts, a film in which a water-repellent agent is coated on an uneven surface has been proposed (Patent Document 5).

  When a sheet or film obtained by coating the above-mentioned paper material or PET resin with an oil repellent is used as food or a packaging material for daily life, food (oil-based liquid) and surfactant adhere to containers and the like using these sheets. There was a problem to do. However, the means described in Patent Documents 1 to 4 cannot sufficiently solve such a problem. Further, even with the means described in Patent Document 5, such a problem cannot be sufficiently solved for an oil-based liquid, a surfactant-based liquid, and the like.

JP 2010-196196 A JP 2009-256506 A JP 2007-291373 A JP 2009-104054 A JP 2008-122435 A

  The present invention has been made in view of the above circumstances, in the main aspect of the present invention, when used as a food container or household goods container, that the oil-based or surfactant-based liquid will adhere. An object is to provide a reduced liquid-repellent resin sheet. It is another object of the present invention to provide a molded article having excellent lyophobicity and oxygen barrier properties obtained by heating and stretching the lyophobic resin sheet.

Means for solving the problem

  That is, the present inventor thought that it is sufficient to impart liquid repellency in order to prevent the adhesion of oil-based liquids and surfactant-based liquids, and as a result of examining various liquid repellency expression means, it was found that polyolefin One surface of the uneven layer containing a crosslinked body of a resin has at least one or more kinds of convex shapes, and the surface having the convex shape has hydrophobic particles containing hydrophobic oxide fine particles and a fluorine-based copolymer resin. The present inventors have found that a liquid-repellent resin sheet provided with a liquid layer can maintain high liquid-repellency while maintaining fine irregularities even after heating and stretching the sheet, and have completed the present invention.

The present invention for solving the above-mentioned problems is constituted by the following.
(1) One surface has an uneven layer having at least one kind of convex shape, the uneven layer contains a crosslinked polyolefin resin, and a hydrophobic oxide is formed on the surface having the convex shape. A liquid-repellent resin sheet provided with a liquid-repellent layer containing fine particles and a fluorine-based copolymer resin.
(2) The liquid-repellent resin sheet according to (1), wherein the uneven layer is crosslinked by irradiating a resin composition containing a polyolefin resin with an electron beam.
(3) The liquid-repellent resin sheet according to (2), wherein the resin composition containing the polyolefin-based resin contains 35 to 100% by mass of the polyolefin-based resin. In another embodiment, the following configuration can be adopted. The liquid-repellent resin sheet according to (1) or (2), wherein the uneven layer containing the crosslinked polyolefin resin is obtained by crosslinking an uneven layer made of 35 to 100% by mass of a polyolefin resin.
(4) A layer made of a resin selected from a styrene-based resin, an olefin-based resin, a polyester-based resin, a nylon-based resin, an ethylene-vinyl alcohol copolymer resin, and an acrylic-based resin on the other surface of the uneven layer. The liquid-repellent resin sheet according to any one of (1) to (3), wherein a base layer having at least one or more is laminated.
(5) A sealant resin layer containing one or two resins selected from a modified olefin-based resin and a hydrogenated styrene-based thermoplastic elastomer is provided between the uneven layer and the base layer. The liquid-repellent resin sheet according to any one of 1) to (4).
(6) The convex shape includes a first convex shape and a second convex shape, and the height of the first convex shape and the height of the second convex shape are each 20 μm to 150 μm, and are adjacent to each other. The liquid-repellent resin sheet according to any one of (1) to (5), wherein an interval between apexes of the convex shape is 20 μm to 100 μm.
(7) The first convex shape and the second convex shape are staggered, and the ratio of the height of the second convex shape to the first convex shape is 0.4 or more and 0.8 or less (6). The liquid-repellent resin sheet according to 1.
(8) The repellent material according to any one of (1) to (7), wherein the crosslinked polyolefin resin is a crosslinked polyolefin resin having a melt mass flow rate at 230 ° C. of 5 g / 10 minutes or more. Liquid resin sheet.
(9) The liquid-repellent resin sheet according to any one of (1) to (8), wherein the hydrophobic oxide fine particles are hydrophobic silica fine particles having a trimethylsilyl group on the surface.
(10) The content of the hydrophobic oxide fine particles in the liquid repellent layer is 20 to 70% by mass, and the content of the fluorine-based copolymer resin is 70 to 30% by mass. The liquid-repellent resin sheet according to any one of (9).
(11) The liquid-repellent resin sheet according to any one of (1) to (10), wherein the thickness of the uneven layer is 50 μm to 200 μm.
(12) Any one of (1) to (11), wherein a contact angle of the surface of the uneven layer with an oil-based liquid or a surfactant-based liquid is 130 ° or more and a falling angle is 40 ° or less. The liquid repellent resin sheet according to one of the above.
(13) A molded product obtained by heating and stretching the liquid-repellent resin sheet according to any one of (1) to (12).
(14) The molded article according to (13), wherein the contact angle between the surface of the uneven layer and the oil-based liquid or the surfactant-based liquid is 120 ° or more and the falling angle is 70 ° or less.
(15) The molded article according to (13) or (14), wherein a decrease rate of the convex height relative to the convex height of the liquid-repellent resin sheet is 30% or less.
(16) A molded article having a flange portion and a bottom portion, wherein the ratio of the thickness of the bottom portion to the thickness of the flange portion is 0.40 to 0.95, any one of (13) to (15). The molded article according to the above.
(17) The molded article according to any one of (13) to (16), which is a container for living goods.
(18) The molded article according to any one of (13) to (16), which is a food container.
(19) A step of forming an irregular shape layer having at least one or more convex shapes on one surface, and the irregular shape layer is made of a resin composition containing a polyolefin-based resin, and is formed on the surface of the irregular shape layer. Irradiating an electron beam to crosslink the polyolefin-based resin, and forming a liquid-repellent layer containing hydrophobic oxide fine particles and a fluorine-based copolymer resin on the convex-shaped surface of the uneven layer. And a method for producing a liquid-repellent resin sheet.

  An uneven layer having at least one or more convex shapes is formed on one surface of the liquid-repellent resin sheet, and the uneven layer contains a crosslinked polyolefin-based resin, and the surface having the convex shape has a hydrophobic property. The liquid-repellent resin sheet provided with a liquid-repellent layer containing oxide fine particles and a fluorine-based copolymer resin has a remarkably improved anti-adhesion property to an oil-based liquid and a surfactant-based liquid on the sheet surface. I found that. Further, they have also found that by including a crosslinked body in a resin forming the uneven layer, liquid repellency can be exhibited even after heating and stretching. Further, at least one layer made of a resin selected from a styrene-based resin, an olefin-based resin, a polyester-based resin, a nylon-based resin, an ethylene-vinyl alcohol copolymer resin, and an acrylic resin is provided on the other surface of the uneven shape layer. By laminating a base layer having at least two layers, oxygen barrier properties and weather resistance are improved. Therefore, the liquid-repellent resin sheet of the present invention and a molded article obtained by heating and stretching the resin sheet can be suitably used for a container for daily necessities and a container for food.

1 is a schematic vertical sectional view showing a liquid-repellent resin sheet according to a first embodiment of the present invention. It is a schematic plan view of the liquid-repellent resin sheet of FIG. FIG. 4 is a schematic vertical sectional view of another embodiment of the liquid-repellent resin sheet according to the first embodiment of the present invention. FIG. 4 is a schematic plan view of the liquid-repellent resin sheet of FIG. 3. FIG. 5 is a schematic vertical cross-sectional view illustrating a laminated structure of a liquid-repellent resin sheet according to a second embodiment of the present invention. It is a schematic longitudinal side sectional view showing the lamination structure of the liquid-repellent resin sheet concerning a third embodiment of the present invention. It is a schematic longitudinal side sectional view showing the lamination structure of the liquid-repellent resin sheet concerning a fourth embodiment of the present invention. This is a container formed by vacuum forming using a liquid-repellent resin sheet.

<Resin sheet>
The liquid-repellent resin sheet (hereinafter, abbreviated as “resin sheet”) according to the present invention has an uneven layer having at least one or more convex shapes formed on one surface of the resin sheet. A liquid-repellent resin sheet containing a crosslinked polyolefin resin and having a liquid-repellent layer containing hydrophobic oxide fine particles and a fluorine-based copolymer resin on a surface having a convex shape. The “crosslinked polyolefin-based resin” means that the polyolefin-based resin contained in the uneven layer forms at least partially a three-dimensional crosslinked structure. The crosslinked body is not limited to the concavo-convex shape layer, and the substrate layer laminated on the other surface of the concavo-convex shape layer may have a crosslinked body as long as the effect of the present invention is not impaired. Hereinafter, various embodiments of the resin sheet will be described, and then a method of manufacturing the resin sheet will be described. However, if the specific description described for one embodiment applies to other embodiments, the other embodiments will be described. Has omitted the description.

  Here, the resin sheet according to the present invention includes not only a non-stretched sheet but also a sheet stretched by heating. Further, in the present invention, the “liquid repellency” of the liquid-repellent resin sheet refers to a liquid repellency sufficient to prevent adhesion of an oil-based liquid and a surfactant-based liquid to the resin sheet. Means gender. Specifically, the contact angle of the liquid to the resin sheet is 130 ° or more, and the falling angle is 40 ° or less. Further, in a molded article obtained by heating and stretching a resin sheet, the contact angle between the surface of the uneven layer on which the liquid-repellent layer is formed and the oil-based liquid or the surfactant-based liquid is 120 ° or more, and the contact angle falls. It shall mean that the angle is 70 ° or less.

  The thickness of this resin sheet is preferably 150 μm to 1200 μm, and more preferably 300 μm to 1000 μm. If it is less than 150 μm, the thickness distribution of the molded product obtained by thermoforming may be poor, and if it exceeds 1200 μm, the production cost of the container may be increased.

[First embodiment]
As shown in FIGS. 1 and 3, the resin sheet according to the first embodiment of the present invention has an uneven shape layer (1a) having at least one or more types of convex shapes on one surface, and has an uneven shape. The layer (1a) contains a crosslinked polyolefin resin. In addition, a liquid-repellent layer (2) is provided on one surface of the convex shape, and the liquid-repellent layer is made of a fluorine-based copolymer resin containing hydrophobic oxide fine particles.

(Uneven shape layer)
The convex shape may be one type of convex shape as shown in FIG. 1, but preferably has a first convex shape and a second convex shape having different shapes as shown in FIG. Further, three or more kinds of convex shapes having different shapes may be provided. Here, the height of the first convex shape is higher than the height of the second convex shape. When the first convex shape and the second convex shape are used, there is no restriction on their arrangement, but it is necessary that the first convex shape and the second convex shape are alternately arranged. Is preferred. The arrangement form of the convex shape is not particularly limited, and there are a grid arrangement and a staggered arrangement arranged vertically and horizontally. To maintain more liquid repellency, the staggered arrangement is preferable.

  The convex shape preferably has a height (h) of 20 μm to 150 μm. If the height of the convex shape is less than 20 μm, the liquid repellency may not be sufficiently ensured. If the height of the convex shape exceeds 150 μm, the dimensions of the uneven shape in the mold for providing the uneven shape become unstable. There are cases. The height of the convex shape is obtained by adding the thickness (100 nm to 4000 nm) of the liquid-repellent layer described later.

  It is preferable that the interval (t) between the vertices of the adjacent convex shapes is 20 μm to 100 μm. Note that the vertex interval is the interval between the vertices of adjacent convex shapes, and means the interval between the convex shapes as long as they are adjacent even if they have different convex shapes. If the apex distance is less than 20 μm, the dimensions of the concavo-convex shape in the mold for providing the concavo-convex shape may become unstable. On the other hand, if it exceeds 100 μm, the liquid repellency may decrease.

  When two types of convex shapes are used, the ratio of the height of the second convex shape to the first convex shape is preferably 0.4 or more and 0.8 or less. By setting the height ratio to 0.4 or more and 0.8 or less, liquid repellency can be more effectively obtained.

  The bottom surface of the convex shape may be a triangular pyramid, a quadrangular pyramid, a hexagonal pyramid, an octagonal pyramid, a pyramid shape such as a cone, a truncated pyramid shape, or a truncated cone shape, but the present inventor has various configurations in the resin sheet according to the present embodiment. As a result of the study, it was found that a convex shape having a hexagonal pyramid shape was particularly preferable.

  The uneven layer contains a crosslinked polyolefin-based resin. It is preferable that the crosslinked polyolefin resin is obtained by crosslinking a resin composition containing 35 to 100% by mass of the polyolefin resin. When the content is 35% by mass or more, the transferability and the crosslinkability of the uneven shape can be improved. Moreover, it is preferable that the crosslinked polyolefin-based resin is obtained by crosslinking a polyolefin-based resin having a melt mass flow rate at 230 ° C. of 5 g / 10 minutes or more. By setting it to 5 g / 10 minutes, the transferability of the uneven shape can be improved.

  The polyolefin resin means a resin made of a polymer containing an α-olefin as a monomer, and particularly preferably contains a polyethylene resin and a polypropylene resin. Examples of the polyethylene resin include a high-density polyethylene, a low-density polyethylene, a linear low-density polyethylene, a linear medium-density polyethylene, and the like. Not only a simple substance, but also a copolymer, graft, or blend having the structure thereof Things are also included. As the latter resin, for example, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic ester copolymer, ethylene-methacrylic ester copolymer, ethylene-vinyl acetate-vinyl chloride copolymer Examples thereof include those obtained by copolymerization and blending of a resin having a polar group in a polyethylene chain, such as a copolymer or a blend of a terpolymer of such a copolymer and an acid anhydride. In consideration of the crosslinkability by electron beam irradiation, it is desirable to use linear low-density polyethylene and linear medium-density polyethylene.

  Examples of the polypropylene-based resin include homopolypropylene, random polypropylene, and block polypropylene. When a homopolypropylene is used, the structure of the homopolypropylene may be any of isotactic, atactic, and syndiotactic. When a random polypropylene is used, the α-olefin to be copolymerized with propylene preferably has 2 to 20 carbon atoms, more preferably 4 to 12 carbon atoms, such as ethylene, 1-butene, 1-pentene, Examples include -hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like. When a block polypropylene is used, a block copolymer (block polypropylene), a block copolymer containing a rubber component, a graft copolymer, or the like can be used. In addition to using these olefin resins alone, other olefin resins can be used in combination. In consideration of the crosslinkability by electron beam irradiation, it is desirable to use random polypropylene or block polypropylene.

  As a method for forming a crosslinked polyolefin-based resin, as described later, a method of irradiating an electron beam to a surface having a convex shape after molding a resin sheet or a polyolefin-based resin composition to which an organic peroxide is added in advance A method in which the resin sheet is formed by heating and humidifying at the time of or after the convex molding of the resin sheet of the product. Among these, it is preferable to form a crosslinked body by irradiation with an electron beam.

  The degree of formation of the crosslinked body can be arbitrarily adjusted depending on the shape of the molded article. The evaluation of the degree of formation of the crosslinked body can be made from the tensile strength change rate before and after electron beam irradiation and the elongation change rate of the molded resin sheet.

(Liquid repellent layer)
The liquid repellent layer contains hydrophobic oxide fine particles and a fluorine-based copolymer resin. The thickness of the liquid-repellent layer is preferably 100 nm to 4000 nm, but is not limited to this numerical range as long as the effects of the present invention can be obtained.

  The hydrophobic oxide fine particles only need to have a hydrophobic group, and may be those that have been made hydrophobic by a surface treatment. For example, it is also possible to use a fine particle silica whose surface state is made hydrophobic by subjecting the hydrophilic oxide fine particle silica to a surface treatment with a silane coupling agent or the like. The type of oxide is not limited as long as it has hydrophobicity. For example, at least one of silica (silicon dioxide), alumina, titania, and silica can be used. These may be known or commercially available ones. For example, as silica, product names “AEROSIL R972”, “AEROSIL R972V”, “AEROSIL R972CF”, “AEROSIL R974”, “AEROSIL RX200”, “AEROSIL RY200” (all manufactured by Nippon Aerosil Co., Ltd.), “AEROSIL R202” "," AEROSIL R805 "," AEROSIL R812 "," AEROSIL R812S ", (above, manufactured by Evonik Degussa). Examples of titania include a product name “AEROXIDE TiO2 T805” (manufactured by Evonik Degussa). Examples of the alumina include fine particles whose surface is made hydrophobic by treating a product name “AEROXIDE Alu C” (manufactured by Evonik Degussa) with a silane coupling agent.

  Among these, specifically, hydrophobic silica fine particles can be suitably used. In particular, hydrophobic silica fine particles having a trimethylsilyl group or a dimethylsiloxane group on the surface are preferable in that higher liquid repellency can be obtained. Examples of commercially available products corresponding to this include “AEROSIL R812”, “AEROSIL R812S”, and “AEROSIL RY300” (all manufactured by Evonik Degussa).

  As the hydrophobic oxide fine particles, those having an average primary particle diameter of 5 nm to 1000 nm are preferable, and those having an average particle diameter of 7 nm to 200 nm are more preferable. By setting the average particle size of the primary particles to 5 nm to 1000 nm, the liquid repellency is improved and the dispersibility in the fluorine-based copolymer resin is improved. The average particle diameter of the primary particles means a numerical value obtained by measuring 3,000 to 5,000 arbitrary particles of the hydrophobic oxide fine particles from an electron micrograph and arithmetically averaging the particle diameters.

  The fluorine-based copolymer preferably contains the copolymer (1) and the copolymer (2). The copolymer (1) and the copolymer (2) can contain the structural units (a) to (d). However, the copolymer (1) contains the structural unit (a) and the structural unit (b), and the copolymer (2) contains the structural unit (a) and the structural unit (c). The copolymer (1) mainly contributes to the development of the liquid repellency of the resin sheet, and the copolymer (2) mainly contributes to the durability of the resin sheet.

  The structural unit (a) is a group in which some or all of the hydrogen atoms of an alkyl group have been substituted with fluorine atoms, and has 1 to 6 carbon atoms. (A) may be a chain polyfluorohydrocarbon group having at least one unsaturated group such as a carbon-carbon unsaturated double bond. As the unsaturated group, (meth) acrylate is preferable.

  The structural unit (b) is preferably a monomer having a saturated hydrocarbon group having 16 to 40 carbon atoms, and is preferably a (meth) acrylate containing an alkyl group having 16 to 40 carbon atoms. More preferred are stearyl (meth) acrylate and behenyl (meth) acrylate.

  The structural unit (c) is a monomer that does not contain a fluorine atom and is derived from a monomer having a crosslinkable functional group. Crosslinkable functional groups include isocyanate groups, blocked isocyanate groups, alkoxysilyl groups, amino groups, alkoxymethylamide groups, silanol groups, ammonium groups, amide groups, epoxy groups, hydroxyl groups, oxazoline groups, carboxyl groups, alkenyl groups And a sulfonic acid group. Further, an epoxy group, a hydroxyl group, a blocked isocyanate group, an alkoxysilyl group, an amino group, and a carboxyl group are more preferable.

  Preferred examples of the monomer forming the structural unit (c) include (meth) acrylates, compounds having two or more copolymerizable groups, vinyl ethers and vinyl esters. The structural unit (c) may be derived from a mixture of two or more types. The structural unit (c) mainly affects the film-forming properties of the liquid-repellent film and the adhesion and adhesion of the liquid-repellent composition to the substrate, and contributes to enhancing the durability.

  The structural unit (d) is a structural unit derived from a monomer having a polymerizable group other than the structural units (a), (b) and (c). In addition, it is preferably one derived from a monomer having good film-forming properties and obtaining a uniform copolymer solution or dispersion. The structural unit (d) is particularly preferably derived from vinyl chloride, vinylidene chloride, cyclohexyl methacrylate, polyoxyethylene di (meth) acrylate, an alkyl ether of polyoxyethylene di (meth) acrylate, or dioctyl maleate. . The structural unit (d) can contribute to improvement in the adhesion of the composition to the substrate and improvement in dispersibility.

  Commercial products corresponding to this include "AG-E070" and "AG-E550D" (manufactured by Asahi Glass Co., Ltd.).

  In the liquid-repellent layer, the content of the hydrophobic oxide fine particles is preferably 20% by mass to 70% by mass, and the content of the fluorine-based copolymer resin is preferably 70% by mass to 30% by mass. By setting the composition in this range, the falling property of the liquid can be obtained. On the other hand, if the content of the hydrophobic oxide fine particles is less than 20% by mass, satisfactory liquid repellency and liquid falling property may not be obtained, and the content of the hydrophobic oxide fine particles is 70% by mass. If it exceeds 300, the hydrophobic oxide fine particles may peel off.

  As a method of forming the liquid-repellent layer on the uneven surface, a dispersion in which hydrophobic oxide fine particles are added to isopropyl alcohol (IPA) is prepared in advance, and then a dispersion with an aqueous dispersion of a fluororesin copolymer is prepared. A method of applying a dispersion liquid adjusted at an arbitrary ratio to the uneven surface with a coater or the like is employed.

[Second embodiment]
As an example of the resin sheet according to the second embodiment of the present invention, as shown in FIG. 5, the uneven layer (1) having the liquid-repellent layer (2) laminated on the surface and the base material layer (4) are used. This is a resin sheet having a sealant resin layer (3) formed therebetween. That is, the layer configuration of the resin sheet according to the second embodiment includes, from top to bottom, a liquid repellent layer (2), an uneven shape layer (1), a sealant resin layer (3), and a base material layer (4). is there. Here, the liquid-repellent layer and the concave-convex-shaped layer are the same as those described in the first embodiment, and a description thereof will be omitted. However, the thickness of the uneven layer is preferably 50 μm to 200 μm. If it is less than 50 μm, the transfer of the uneven shape may be poor. On the other hand, if it exceeds 200 μm, the production cost may increase.

(Base material layer)
The base material layer is made of styrene resin (impact polystyrene, polybutadiene-polystyrene-polyacrylonitrile graft polymer, etc.), olefin resin (polyethylene, polypropylene, etc.), polycarbonate, polyester resin (polyethylene terephthalate, polybutylene terephthalate, etc.) And thermoplastic resins such as nylon resins (nylon 6, nylon-66, etc.), ethylene-vinyl alcohol copolymers, and acrylic resins. When laminating, there are lamination by co-extrusion molding, extrusion lamination molding using a non-stretched film, biaxially stretched film, and lamination by dry lamination molding.

  As the styrenic resin, preferably, 60% to 15% by mass, more preferably 55% to 15% by mass of a polystyrene resin, and 40% to 85% by mass, more preferably 45% to 85% by mass And a high-impact polystyrene resin.

  Examples of the polyester-based resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, polymethylene terephthalate, and diol components such as diethylene glycol, neopentyl glycol, and polyalkylene glycol as copolymerization components, and adipic acid. And a polyester resin copolymerized with a dicarboxylic acid component such as sebacic acid, phthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid.

  Examples of the nylon-based resin include lactam polymers such as caprolactam and laurolactam; polymers of aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid; hexamethylenediamine, decamethylenediamine, dodeca Aliphatic diamines such as methylenediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane) Adicyclic units such as alicyclic diamines, aromatic diamines such as m- or p-xylylenediamine, and alicyclic dicarboxylic acids such as adipic acid, suberic acid, and sebacic acid; and cyclohexanedicarboxylic acids. Acid, terephthalic acid, aromatic dicarboxylic acid such as isophthalic acid, etc. Polycondensates of carboxylic acid units; and copolymers thereof. Specifically, nylon 6, nylon 9, nylon 11, nylon 12, nylon 66, nylon 610, nylon 611, nylon 612, nylon 6T, nylon 6I, nylon MXD6, nylon 6/66, nylon 6/610, nylon 6 / 6T and nylon 6I / 6T, among which nylon 6 and nylon MXD6 are preferred.

  The structure of the acrylic resin is not particularly limited as long as it is a vinyl polymer based on a methacrylic acid ester monomer. Examples of the methacrylate monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, and hexyl methacrylate. Of these, methyl methacrylate is particularly preferred. Further, the alkyl group such as a propyl group, a butyl group, a pentyl group, and a hexyl group in the methacrylic acid ester monomer may be linear or branched. In addition, the methacrylate resin blended in the resin composition of the present embodiment may be a homopolymer of a methacrylate monomer or a copolymer of a plurality of methacrylate monomers. Alternatively, it may have a monomer unit derived from a known vinyl compound other than methacrylic acid ester, such as ethylene, propylene, butadiene, styrene, α-methylstyrene, acrylonitrile, and acrylic acid.

  In the substrate layer, if necessary, a pigment, a coloring agent such as a dye, a release agent such as a silicone oil, a fibrous reinforcing agent such as a glass fiber, a talc, a clay as long as the effects of the present invention are not impaired. , A colorant such as silica, a salt compound of sulfonic acid and an alkali metal, an antistatic agent such as polyalkylene glycol, and an additive such as an ultraviolet absorber and an antibacterial agent. Further, the scrap resin generated in the production process of the multilayer resin sheet of the present invention can be mixed and used.

(Sealant resin layer)
The sealant resin layer develops adhesiveness between the uneven layer and the substrate layer. As the resin component, there are 100% by mass of a modified olefin resin or 100% by mass of a hydrogenated styrene-based thermoplastic elastomer.

  Examples of the modified olefin-based resin include olefins having about 2 to 8 carbon atoms such as ethylene, propylene, and butene-1; those olefins and ethylene, propylene, butene-1, 3-methylbutene-1, pentene-1, 4- Copolymers with other olefins having about 2 to 20 carbon atoms, such as methylpentene-1, hexene-1, octene-1, and decene-1, and vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, and acrylic acid esters Olefin resins, such as copolymers with vinyl compounds such as methacrylic acid esters and styrene; ethylene-propylene copolymers, ethylene-propylene-diene copolymers, ethylene-butene-1 copolymers, propylene-butene- Olefin-based rubber such as 1 copolymer is used for acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, Acids, fumaric acid, itaconic acid, citraconic acid, unsaturated carboxylic acids such as tetrahydrophthalic acid, or derivatives thereof such as acid halides, amides, imides, anhydrides and esters, specifically, maleenyl chloride, maleimide, anhydride Typical examples include those modified with maleic acid, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, etc. under grafting conditions.

  Among them, "ethylene-propylene-diene copolymer" or "ethylene-propylene or butene-1 copolymer rubber" modified with unsaturated dicarboxylic acid or its anhydride, particularly maleic acid or its anhydride, is preferable. .

  Examples of the hydrogenated styrene-based thermoplastic elastomer include a hydrogenated product of a copolymer of a styrene-based monomer and butadiene or isoprene, and a hydrogenated product of a styrene-butadiene-styrene block copolymer (styrene-ethylene / butylene-styrene block copolymer). Polymer) and hydrogenated styrene-isoprene-styrene block copolymer (styrene-ethylene-propylene-styrene block copolymer). Among these, a styrene-ethylene / butylene-styrene block copolymer is particularly preferred.

  The thickness of the sealant resin layer is preferably from 20 μm to 90 μm, more preferably from 40 μm to 80 μm. When it is less than 20 μm, delamination may occur between the uneven layer and the base material layer, and when it exceeds 90 μm, the production cost may increase.

[Third embodiment]
As shown in FIG. 6, the resin sheet according to the third embodiment of the present invention does not use the sealant resin layer (3) shown in the second embodiment, but uses the uneven layer (1) and the base material layer (4). ) Are directly laminated. That is, the layer configuration of the resin sheet according to the third embodiment is, from top to bottom, a liquid-repellent layer (2), an uneven shape layer (1), and a base material layer (4). It has a layer configuration in which the sealant resin layer is removed from such a thermoplastic resin sheet. Here, the liquid-repellent layer and the concavo-convex shape layer are the same as the layers in the first embodiment and the second embodiment, and the description is omitted. On the other hand, it is preferable that the base material layer (4) in the present embodiment has sufficient adhesiveness to the uneven shape layer.

  Therefore, in the resin sheet according to the third embodiment, it is preferable to use, as the base material layer, a styrene-based resin having excellent adhesion to the uneven layer. A styrene resin composition to which a hydrogenated styrene thermoplastic elastomer is added can also be used. When the impact-resistant polystyrene resin and the hydrogenated styrene-based thermoplastic elastomer are used in combination, 5 to 10 parts by mass of the hydrogenated styrene-based heat-resistant resin is used for 90 to 95 parts by mass of the impact-resistant polystyrene resin. It is preferable to add a plastic elastomer. In this case, if the addition amount of the hydrogenated styrene-based thermoplastic elastomer is less than 5 parts by mass, the adhesion to the uneven layer may be insufficient, and delamination may occur. May be higher.

[Fourth embodiment]
As shown in FIG. 7, the resin sheet according to the fourth embodiment of the present invention includes a liquid-repellent layer (2), an uneven layer (1), a first sealant resin layer (3a), an oxygen barrier base material layer ( 5) A resin sheet laminated in the order of the second sealant resin layer (3b) and the base material layer (4). The first sealant resin layer and the second sealant resin layer may have the same or different compositions. The thickness of the uneven layer is preferably 50 μm to 250 μm. If it is less than 50 μm, the transfer of the uneven shape may be poor. On the other hand, if it exceeds 200 μm, the production cost may increase.

(Oxygen barrier substrate layer)
Examples of the oxygen barrier substrate layer include an ethylene-vinyl alcohol copolymer resin and a nylon-based resin. Among them, an ethylene-vinyl alcohol copolymer resin is preferable in view of workability and moldability.

  The ethylene-vinyl alcohol copolymer resin is usually obtained by saponifying an ethylene-vinyl acetate copolymer, and has an oxygen barrier property, processability, and moldability. % To 65 mol%, preferably 20 mol% to 50 mol%, and a saponification degree of 90% or more, preferably 95% or more.

  Examples of the nylon resin include lactam polymers such as caprolactam and laurolactam; polymers of aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid; hexamethylenediamine, decamethylenediamine , Dodecamethylenediamine, aliphatic diamines such as 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexyl) Alicyclic diamines such as methane), diamine units such as aromatic diamines such as m- or p-xylylenediamine, and alicyclic rings such as aliphatic dicarboxylic acids such as adipic acid, suberic acid and sebacic acid, and cyclohexanedicarboxylic acid. Aromatic dicarboxylic acids such as formula dicarboxylic acid, terephthalic acid and isophthalic acid Polycondensates of a dicarboxylic acid unit and the like, and copolymers thereof, and the like.

  Specific examples of the nylon resin include nylon 6, nylon 9, nylon 11, nylon 12, nylon 66, nylon 610, nylon 611, nylon 612, nylon 6T, nylon 6I, nylon MXD6, nylon 6/66, and nylon 6. / 610, nylon 6 / 6T, nylon 6I / 6T and the like, and among them, nylon 6 and nylon MXD6 are preferable.

(Sealant resin layer)
As the sealant resin layer, a modified olefin resin is preferable. Examples of the modified olefin-based resin include homopolymers of olefins having about 2 to 8 carbon atoms such as ethylene, propylene and butene-1; homopolymers of these olefins and ethylene, propylene, butene-1, 3-methylbutene- 1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, copolymers with other olefins having about 2 to 20 carbon atoms such as decene-1, vinyl acetate, vinyl chloride, acrylic Olefinic resins such as copolymers with vinyl compounds such as acid, methacrylic acid, acrylic acid ester, methacrylic acid ester and styrene; ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-butene-1 Olefinic rubbers such as copolymers, propylene-butene-1 copolymers, etc. Unsaturated carboxylic acids such as isocrotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and tetrahydrophthalic acid, or derivatives thereof such as acid halides, amides, imides, anhydrides, and esters, specifically, maleenyl chloride Typical examples thereof include those modified with maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, etc. under grafting reaction conditions.

  Of these, an ethylene resin, a propylene resin, or an ethylene-propylene or butene-1 copolymer rubber modified with an unsaturated dicarboxylic acid or an anhydride thereof, particularly, maleic acid or an anhydride thereof is preferable.

  The thickness of the sealant resin layer on each side is preferably 10 μm to 50 μm, more preferably 20 μm to 40 μm. If it is less than 10 μm, sufficient interlayer adhesion strength may not be obtained, and if it is more than 50 μm, production cost may be increased.

<Manufacture of liquid-repellent resin sheet>
The method for producing the resin sheet according to the present invention is not limited, and any method may be used. Typically, the method includes a single-layer sheet having at least one or more kinds of convex shapes on one surface or the uneven layer. Forming a laminated resin sheet, then cross-linking the uneven layer, and forming a liquid-repellent layer on the surface.

  First, in producing a single-layer sheet having at least one kind of convex shape on one surface or a multilayer resin sheet including the uneven layer, any resin sheet molding method can be used. For example, a single-layer extruder is used for a single layer, and a plurality of single-axis extruders is used for a multi-layer. Can be In the case of a multilayer, a multi-manifold die may be used. The layer configuration of each embodiment of the resin sheet of the present invention is basically the same as described above. In addition, for example, the scrap raw material generated in the manufacturing process of the resin sheet of the present invention or the molded container is made of a material having physical properties. As long as no deterioration such as the above is observed, it may be added to the base material layer or may be laminated as a further layer.

  Next, a concavo-convex shape is formed on the single-layer or multi-layer resin sheet. This method is not particularly limited, and any method known to those skilled in the art can be used. For example, there are a method of manufacturing using an extrusion molding method, a method of manufacturing using a photolithography method, a method of manufacturing using a hot press method, a method of manufacturing using a pattern roll and a UV curable resin, and the like.

  Next, a crosslinked body is formed in the uneven layer in order to maintain the uneven shape of the uneven layer even after molding and maintain desired liquid repellency. In this crosslinking treatment, it is preferable to irradiate an electron beam to the surface of the resin sheet on which the uneven layer is present. That is, as described above, the uneven layer is formed using a composition containing a polyolefin-based resin. As the polyolefin, polyethylene and polypropylene are preferable. Polyolefin is a crosslinked polymer in which molecular chain crosslinking proceeds preferentially by electron beam irradiation, like polyvinylidene fluoride, polymethyl acrylate, polyvinyl chloride, polybutadiene, vinyl alcohol, polyamide and the like. Among them, linear low-density polyethylene, linear medium-density polyethylene, random polypropylene, and block polypropylene are easily crosslinked, and in particular, linear low-density polyethylene is most easily crosslinked. Therefore, when the sheet surface on which the uneven shape layer exists is irradiated with an electron beam, the uneven shape layer can be made into a crosslinked body.

  The conditions for electron beam irradiation of the polyolefin-based resin composition are preferably an acceleration voltage of 110 kV to 210 kV and a dose of 120 kGy to 350 kGy. By irradiating the surface of the uneven sheet with an electron beam in this condition range, it is possible to obtain a crosslinked body which maintains the uneven shape even after molding. In addition, in the case of a single layer, even if irradiation is performed on the entire concavo-convex sheet, the amount of electron beam irradiation on the opposite surface where the concavo-convex shape is formed is small, so there is no risk of affecting physical properties and the like. In this case, even if the irradiation is performed beyond the uneven layer, the amount of electron beam irradiation on the sealant resin layer and the like becomes small, and there is no possibility of affecting the interlayer adhesion and the like. On the other hand, under the irradiation condition weaker than this condition, the uneven portion of the uneven layer cannot be cross-linked to such an extent that the shape is almost maintained even after the heat stretching, while the irradiation condition stronger than this condition is used. In this case, there is a possibility that the sealing property with the lid material for packaging may be poor (sufficient peel strength may not be generated). Here, the degree of crosslinking of the concave-convex layer is not particularly limited, but the height of the convex shape is sufficiently maintained after the resin sheet is formed, and the reduction rate of the height is preferably 30% or less, more preferably. Is crosslinked to an extent of 25% or less, more preferably 20% or less. In a container formed of a sheet satisfying this condition, a desired liquid repellency can be obtained in combination with the above liquid repellent layer.

  Finally, a liquid-repellent layer is formed on the surface of the uneven layer. The method for forming the liquid-repellent layer is not particularly limited, and for example, a known coating method such as roll coating, gravure coating, bar coating, doctor blade coating, brush coating, and powder electrostatic method can be employed. The solvent used in preparing the coating liquid is not particularly limited. In addition to water, for example, alcohol (ethanol), cyclohexane, toluene, acetone IPA, propylene glycol, hexylene glycol, butyl diglycol, pentamethylene glycol, normal Organic solvents such as pentane, normal hexane, and hexyl alcohol can be appropriately selected. At this time, a trace amount of a dispersant, a coloring agent, an anti-settling agent, a viscosity modifier and the like can be used in combination.

  Note that, in the above description, an example in which the cross-linking treatment of the uneven layer by electron beam irradiation is performed before forming the liquid-repellent layer on the uneven layer, but the liquid-repellent layer is laminated on the uneven layer. After that, a crosslinking treatment may be performed.

<Molded product>
The molded article of the present invention is obtained by molding the resin sheet of the present invention. As a molding method, general vacuum molding, air pressure molding, and as these applications, a plug assist method in which a plug is brought into contact with one side of a sheet to perform molding, or a pair of male and female molds are brought into contact with both sides of the sheet. And a method called so-called match molding, which is not limited thereto. In addition, as a method of heating and softening the sheet before molding, a known sheet heating method such as radiant heating using an infrared heater or the like, which is non-contact heating, can be applied.

The reduction ratio of the convex height to the convex height of the resin sheet is preferably 30% or less, more preferably 25% or less, and further preferably 20% or less. By setting the reduction rate to 30% or less, a desired liquid repellency can be obtained in the container. The rate of decrease in the height of the convex shape can be calculated by the following formula by measuring the height of the convex shape of the bottom surface of the resin sheet used for molding and the molded tray container using a laser microscope or the like.
Reduction rate of the height of the convex shape = [(the height of the convex portion of the resin sheet) − (the height of the convex portion of the bottom of the tray container)] / the height of the convex portion of the resin sheet × 100 (%)
As described above, by adjusting the conditions (acceleration voltage, dose) of electron beam irradiation at the time of crosslinking, the unevenness after molding can be maintained, and the rate of change in the height of the convexity can be reduced. .

  When the molded product has a flange portion and a bottom portion, the ratio of the thickness of the bottom portion to the thickness of the plunge portion is preferably 0.40 to 0.95. By adjusting the thickness ratio within this range, the desired lyophobic property of the container can be obtained.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the examples and the like.

Various raw materials used in Examples and the like are as follows.
(1) Concavo-convex layer (A-1) Random polypropylene "PM921V" (manufactured by Sun Allomer)
(A-2) Block polypropylene "PM854X" (manufactured by Sun Allomer)
(B-1) Linear medium-density polyethylene resin (C4) "Neozex 45200" (manufactured by Prime Polymer Co., Ltd.)
(B-2) Linear low-density polyethylene resin (C6) "Ultzex 20200J" (manufactured by Prime Polymer Co., Ltd.)
(C) Styrene-conjugated diene block copolymer resin “730L” (manufactured by Denki Kagaku Kogyo KK) (diene content 25% by mass)
(D) GPPS resin "G100C" (Toyo Styrene)

(2) Liquid repellent layer (E) Hydrophobic oxide fine particles: hydrophobic silica "AEROSIL R812S" (manufactured by Evonik Degussa)
(F-1) Fluorine copolymer resin: "AG-E070" (manufactured by Asahi Glass Co., Ltd.)
(F-2) Fluorine copolymer resin: "AG-E550D" (manufactured by Asahi Glass Co., Ltd.)

(3) Sealant resin layer (G) Hydrogenated styrene-based thermoplastic elastomer "Tuftec P2000" (made by Asahi Kasei Corporation)
(H) Hydrogenated styrene-based thermoplastic elastomer "Tuftec M1943" (manufactured by Asahi Kasei Corporation)
(I) Modified olefin resin "Modic F502" (Mitsubishi Chemical Corporation)
(J) Modified olefin resin "Admer SE810" (manufactured by Mitsui Chemicals, Inc.)
(K) HIPS resin "Toyostyrol H850N" (Toyo Styrene Co., butadiene content 9.0 mass%)

(4) Substrate layer (H) Hydrogenated styrene-based thermoplastic elastomer “TUFTEC M1943” (manufactured by Asahi Kasei Corporation)
(K) HIPS resin "Toyostyrol H850N" (Toyo Styrene Co., butadiene content 9.0 mass%)
(L) GPPS resin "HRM23" (manufactured by Toyo Styrene Co., Ltd.)
(M) PET resin "TRN-8550FF" (manufactured by Teijin Limited)
(N) Nylon 6 resin "1022B" (manufactured by Ube Industries)
(O) Ethylene-vinyl alcohol copolymer "EVAL J-171B" (manufactured by Kuraray Co., Ltd.)
(P) Acrylic resin "HBS000" (Mitsubishi Chemical Corporation)
(Q) Polycarbonate resin "L-1225L" (manufactured by Teijin Limited)

  The methods for evaluating various characteristics of the resin sheets produced in the examples and the comparative examples and the containers molded using the resin sheets are as follows.

(1) Height of convex shape, interval between convex vertices The convex shape of the sheet and the convex height and convex interval of the convex portion of the bottom portion of the molded tray container (see FIG. 8) are measured using a laser microscope VK-X100 (manufactured by Keyence Corporation). ). In addition, what measured the cross section of the uneven | corrugated shape using the microtome was used for the measured sample. As for the height of the convex shape, 10 heights having the same shape were measured from arbitrary three places of the sheet and the molded product, and the arithmetic average of the 30 measured values was used. When there were two or more types of convex shapes, the heights of the first convex shape and the second convex shape were obtained by the same method for each. Regarding the vertex interval, the vertex interval of ten adjacent convex shapes was measured from any three places of the sheet and the molded product, and the arithmetic average of the 30 measured values was used. When there were two or more types of convex shapes, the vertex interval between the first convex shape and the second convex shape was measured, and the arithmetic average of the 30 measured values was used.

(2) Contact Angle and Fall Angle The contact angle and the fall angle were measured for the sheet and the bottom of the molded tray container using an automatic contact angle meter DM-501 (manufactured by Kyowa Interface Science Co., Ltd.). The test solution was salad oil (Nissin Oillio Group), hand soap "Kireikirei" (manufactured by Lion), milky lotion "Snow Gokochi" (Rohto Pharmaceutical), and paint "black" (manufactured by Pentel). Was 8 μL when measuring the contact angle and 20 μL when measuring the falling angle.
In the case of a sheet, if the contact angle is 130 ° or more, it can be determined that the liquid repellency is high and the adhesion of the liquid can be prevented. When the falling angle is 40 ° or less, the liquid repellency is high, and it can be determined that the adhesion of the liquid can be prevented. In the case of a tray container, if the contact angle is 120 ° or more, the liquid repellency is high, and it can be determined that liquid adhesion can be prevented. When the falling angle is 70 ° or less, it can be determined that the liquid repellency is high and the adhesion of the liquid can be prevented.

(3) Evaluation of Sealability A flange portion (see FIG. 8) of the molded tray container was cut out, and heat sealing was performed using a heat seal tester (manufactured by Sagawa Seisakusho). The heat seal tester uses a seal iron with a width of 1.0 mm. The sealing material is a lid material used for a milk portion container (based on a laminate of PET resin and aluminum foil, and an acrylic resin or a sealant agent). A lid material using a polyester resin, thickness: 80 μm) was used. The sealing temperature is 210 ° C. and the sealing pressure is 0.36 MPa. The peel strength was measured using a strograph VE1D (manufactured by Toyo Seiki Co., Ltd.) with a lid material sandwiched between one chuck portion of the strograph and a sheet sample sandwiched with the other chuck portion. The peeling speed is 200 mm / min. When the peel strength is 2.8 N or more, it can be determined that the sealability is good.

(4) Thickness ratio The thickness of the bottom portion (see FIG. 8) with respect to the thickness of the flange portion of the molded tray container was calculated by the following equation.
Thickness ratio = Bottom thickness / Flange thickness

(5) Decrease rate of the height of the convex shape The decrease rate of the height of the convex shape is obtained by measuring the height of the convex shape at the bottom of the resin sheet used for molding and the molded tray container using a laser microscope. It was calculated by the formula. When the decrease rate is 30% or less, it can be determined that the uneven shape is maintained before and after molding.
Reduction rate of the height of the convex shape = [(the height of the convex portion of the resin sheet) − (the height of the convex portion of the bottom of the tray container)] / the height of the convex portion of the resin sheet × 100 (%)

(6) Melt mass flow rate Measured under the conditions of a test temperature: 230 ° C. and a load: 2.16 Kg in accordance with JIS K 7210. The test equipment used was a melt indexer F-F01 (manufactured by Toyo Seiki Seisaku-sho, Ltd.).

(7) Oxygen Permeability The oxygen permeability of the sheet was measured using an OX-TRAN oxygen permeability measuring device (manufactured by Mocon) in accordance with JIS K7126-B method at a temperature of 25 ° C. and a relative humidity of 65%. Measured below. If the oxygen permeability is less than 3.0 ml / m ² · day · atm, it can be determined that the oxygen barrier property is good.

<Example 1 (layer configuration in FIG. 1)>
Using a single 65 mm single screw extruder, the resin sheet was extruded by the T-die method. The extruded sheet was cast with a transfer roll and a touch roll having a surface with an uneven shape by a laser engraving method to obtain a resin sheet including an uneven layer having an uneven surface.

  The resin sheet provided with the concavo-convex shape obtained above is irradiated with an electron beam using an electron beam irradiation apparatus (manufactured by Iwasaki Electric Co., Ltd.) under irradiation conditions of an acceleration voltage of 200 kV and a dose of 250 kGy, and a cross-linking treatment of the concavo-convex layer Was carried out. When the elongation at break of the resin sheet before and after electron beam irradiation was measured, the elongation at break before electron beam irradiation was 700%, but the elongation at break after electron beam irradiation was 10%. The elongation at break was such that five JIS No. 2 dumbbells punched out in the extrusion direction of the resin sheet were prepared, and were broken at a pulling rate of 10 mm / min at 23 ± 1 ° C. and a relative humidity of 50 ± 2 ° C. It is the value obtained by arithmetically averaging the elongation percentage before performing.

  Next, in order to form a liquid-repellent layer on the surface of the uneven layer, hydrophobic silica and a fluorine-based copolymer resin were used. The hydrophobic silica in the liquid-repellent layer was 66% by mass, and the fluorine-based copolymer resin was 34%. A dispersion liquid (solvent: a mixed liquid of purified water / isopropyl alcohol) was prepared by mixing so as to have a mass%. Using a bar coater, this mixed dispersion was coated on the surface of the corrugated uneven layer, and dried at 90 ° C. to 150 ° C. to form a liquid-repellent layer. Table 1 shows the composition of the resin sheet having the liquid-repellent layer formed on the surface of the uneven layer.

  Various characteristics of the resin sheet produced as described above and the formed tray container were evaluated by the above-described methods. The results are shown in Tables 2 and 3.

<Examples 2 to 12, Comparative Examples 1 to 7>
The resin sheets according to Examples 2 to 12 and Comparative Examples 1 to 7 were prepared in the same manner as in Example 1 except that the composition, thickness, and MFR of the uneven layer and the liquid-repellent layer were set as shown in Table 1. Further, an evaluation test similar to that in Example 1 was performed using the tray container formed with the resin sheet, and the results are shown in Tables 2 and 3.

  In Comparative Example 1, no liquid-repellent layer was formed, and in Comparative Example 2, no unevenness was provided. Comparative Example 3 does not contain hydrophobic silica, and Comparative Example 4 has a composition in which no fluorinated copolymer resin is used in the liquid-repellent layer. Comparative Example 5 is a composition using silica which has not been subjected to a hydrophobic surface treatment for the liquid repellent layer, and Comparative Example 6 is a composition using only a HIPS resin in a bell-shaped resin sheet having a concave-convex shape. 7 does not perform electron beam irradiation.

  From the results shown in Table 2, the following became clear. In all of Examples 1 to 12, results were obtained that satisfied all of the evaluation criteria relating to the liquid repellency (contact angle, falling angle) and the reduction rate of the convex shape height for each liquid in the resin sheet. In contrast, in Comparative Examples 1 to 4, 6, and 7, liquids other than purified water did not roll on the resin sheet. In Comparative Example 5, all the liquid did not roll.

Example 13 (Layer Configuration in FIG. 5)
Using a single 40 mm single screw extruder and a feed block method, a multilayer resin having a thickness of 500 μm and a layer configuration of 80 μm of an uneven shape layer, 40 μm of a sealant resin layer, and 380 μm of a base material layer (nylon resin) in this order. The sheet was extruded by a T-die method.

  The extruded sheet obtained above was cast with a transfer roll and a touch roll having an uneven surface on the surface by laser engraving to obtain a multilayer resin sheet having an uneven surface on the sheet.

  The resin sheet provided with the concavo-convex shape obtained above is irradiated with an electron beam using an electron beam irradiation apparatus (manufactured by Iwasaki Electric Co., Ltd.) under irradiation conditions of an acceleration voltage of 200 kV and a dose of 250 kGy, and a cross-linking treatment of the concavo-convex layer Was carried out.

  Next, in order to form a liquid-repellent layer on the surface of the uneven layer, hydrophobic silica and a fluorine-based copolymer resin were added so that the hydrophobic silica was 66% by mass and the fluorine-based copolymer resin was 34% by mass. (A solvent is a mixed solution of purified water and isopropyl alcohol). Using a bar coater, this mixed dispersion was coated on the surface of the corrugated uneven layer, and dried at 90 ° C. to 150 ° C. to form a liquid-repellent layer. Table 4 shows the composition and layer configuration of each layer of the resin sheet having the liquid-repellent layer formed on the surface of the uneven layer.

  Various characteristics of the resin sheet produced as described above and the formed tray container were evaluated by the methods described above. The results are shown in Tables 5 and 6.

<Examples 14 to 24, Comparative Examples 8, 10 to 14>
Examples 14 to 24 and Comparative Example 8 were performed in the same manner as in Example 13 except that the composition, thickness, and MFR of each layer of the uneven layer, the liquid-repellent layer, and other multilayer resin sheets were set as shown in Table 4. , 10-14. The same evaluation test as that in Example 13 was performed using the tray container formed with the resin sheet, and the results are shown in Tables 5 and 6.

  In Comparative Example 9, no oil-repellent layer was formed. In Comparative Example 10, since the polyethylene having an MFR of 1.1 g / 10 min was used for the uneven layer, transferability was poor, and Comparative Example 11 was a composition in which hydrophobic silica was not used for the liquid-repellent layer. Comparative Example 12 is a composition using no fluorine-based copolymer resin in the liquid-repellent layer, and Comparative Example 13 is a composition using silica not subjected to hydrophobic surface treatment in the liquid-repellent layer. 14 does not perform electron beam irradiation.

  From the results shown in Tables 5 and 6, the following became clear. In all of Examples 13 to 24, results satisfying all the evaluation criteria relating to the liquid repellency (contact angle, falling angle), the height reduction rate of the convex shape, and the sealing property with respect to each liquid in the resin sheet were obtained. On the other hand, in Comparative Examples 8, 10 to 12, and 14, liquids other than purified water did not roll. Further, in Comparative Example 13, all the liquid did not roll, and sealing was not possible due to the high dose (the convex shape was not crushed by the seal iron).

Example 25 (Layer Configuration in FIG. 6)
Using two 40 mm single screw extruders, a 700 μm-thick resin sheet having a layer configuration of a concavo-convex layer of 90 μm and a base layer of 610 μm was extruded from a T-die by a feed block method. In addition, what mixed the impact-resistant polystyrene resin and the hydrogenated styrene thermoplastic elastomer by mass ratio 95/5 (HIPS / hydrogenated styrene thermoplastic elastomer) was used as a base material layer. The same evaluation test as in Example 13 was performed on the extruded sheet obtained above. The results are shown in Tables 5 and 6.

<Example 26, Comparative example 9>
The resin sheets according to Example 26 and Comparative Example 9 were prepared in the same manner as in Example 25 except that the composition, thickness, and MFR of the uneven layer, the liquid-repellent layer, and the styrene-based resin layer were set as shown in Table 3. Tables 5 and 6 show the results of the evaluation. Note that Comparative Example 9 is a composition having no concavo-convex shape.

  From the results shown in Tables 5 and 6, the following became clear. In Examples 25 to 26, results were obtained that satisfied all of the evaluation criteria regarding the liquid repellency (contact angle, falling angle), the reduction rate of the height of the convex shape, and the sealing property with respect to each liquid on the resin sheet. On the other hand, in Comparative Example 9, the liquid other than the purified water did not fall.

<Example 27 (layer configuration in FIG. 7)>
Using five 40 mm single-screw extruders, a feed block method was used to form an uneven layer 80 μm, a first sealant resin layer 10 μm, an oxygen barrier resin layer 15 μm, a second sealant resin layer 10 μm, and a substrate layer 385 μm. A multilayer resin sheet having a thickness of 500 μm and having this order was extruded from a T-die.

  The extruded sheet obtained above was cast with a transfer roll and a touch roll having an uneven surface on the surface by laser engraving to obtain a resin sheet having an uneven surface on the sheet.

  The resin sheet provided with the concavo-convex shape obtained above is irradiated with an electron beam using an electron beam irradiation apparatus (manufactured by Iwasaki Electric Co., Ltd.) under irradiation conditions of an acceleration voltage of 200 kV and a dose of 250 kGy, and a crosslinking treatment of the concavo-convex layer Was carried out.

  Next, in order to form a liquid-repellent layer on the surface of the uneven layer, hydrophobic silica and a fluorine-based copolymer resin were added so that the hydrophobic silica was 66% by mass and the fluorine-based copolymer resin was 34% by mass. (A solvent is a mixed solution of purified water and isopropyl alcohol). Using a bar coater, this mixed dispersion was coated on the surface of the corrugated uneven layer, and dried at 90 ° C. to 150 ° C. to form a liquid-repellent layer. Table 7 shows the configuration of each layer, and Tables 8 and 9 show the evaluation results.

<Examples 28 to 39, Comparative Examples 15 to 21>
Examples 28 to 39 and Comparative Examples 15 to 39 were performed in the same manner as in Example 27, except that the composition, thickness, and MFR of each layer of the uneven shape layer, the liquid repellent layer, and other multilayer resin sheets were set as shown in Table 7. The resin sheet according to No. 21 was produced.

  In Comparative Example 15, no liquid-repellent layer was formed, and in Comparative Example 16, no irregularities were provided. In Comparative Example 17, since the polyethylene having an MFR of 1.1 g / 10 min was used for the uneven layer, the transferability was poor. In Comparative Example 18, the liquid-repellent layer had no hydrophobic silica. Comparative Example 19 was a composition using no fluorine-based copolymer, Comparative Example 20 was a composition using silica that had not been subjected to a hydrophobic surface treatment for the liquid-repellent layer, and Comparative Example 21 was an electron beam-irradiated layer. Has not been implemented.

  From the results shown in Tables 8 and 9, the following became clear. In all of Examples 27 to 39, results satisfying all the evaluation criteria relating to the liquid repellency (contact angle, falling angle), the reduction rate of the convex shape height, the sealing property, and the oxygen barrier property with respect to each liquid in the sheet were obtained. Was done. On the other hand, in Comparative Examples 15 to 19 and 21, liquids other than purified water did not fall. Further, in Comparative Example 20, all the liquid did not roll, and sealing was not possible due to the high dose (the convex shape was not crushed by the seal iron).

  As described above, the present invention has been described using various embodiments, but it is needless to say that the technical scope of the present invention is not limited to the scope described in the above embodiments. It is apparent to those skilled in the art that various changes or improvements can be made to the above embodiment. It is apparent from the description of the appended claims that embodiments with such modifications or improvements can be included in the technical scope of the present invention.

DESCRIPTION OF SYMBOLS 1 Concavo-convex shape layer 1a Convex shape 1b Convex part vertex 1c First convex shape 1d Second convex shape h Convex shape height t Convex shape vertex interval 2 Liquid repellent layer 3 Sealant resin layer 3a First sealant resin layer 3b 2 sealant resin layer 4 substrate layer 5 oxygen barrier substrate layer 6 flange 7 bottom

Claims (19)

On one surface, an irregular shape layer having at least one or more convex shapes is provided, wherein the irregular shape layer contains a crosslinked polyolefin-based resin, and the surface of the convex shape has hydrophobic oxide fine particles and A liquid-repellent layer containing a fluorine-based copolymer resin is provided , and the surface of the uneven layer has a contact angle of 130 ° or more when it comes into contact with an oil-based liquid or a surfactant-based liquid, and a falling angle is reduced. A liquid-repellent resin sheet having an angle of 40 ° or less . On one surface, an irregular shape layer having at least one or more convex shapes is provided, wherein the irregular shape layer contains a crosslinked polyolefin-based resin, and the surface of the convex shape has hydrophobic oxide fine particles and A liquid-repellent layer containing a fluorine-based copolymer resin , wherein the crosslinked polyolefin-based resin is a crosslinked body of a polyolefin-based resin having a melt mass flow rate at 230 ° C. of 5 g / 10 minutes or more ; Resin sheet. The liquid-repellent resin sheet according to claim 1 or 2 , wherein the uneven layer is formed by irradiating a resin composition containing a polyolefin-based resin with an electron beam to crosslink the resin composition. The liquid-repellent resin sheet according to claim 3 , wherein the resin composition containing the polyolefin-based resin contains 35 to 100% by mass of the polyolefin-based resin. On the surface opposite to the surface having the convex shape of the uneven shape layer, a styrene resin, an olefin resin, a polyester resin, a nylon resin, an ethylene-vinyl alcohol copolymer resin, and an acrylic resin are selected. The liquid-repellent resin sheet according to any one of claims 1 to 4 , wherein a base material layer having at least one resin layer is laminated. The method according to claim 5 , further comprising a sealant resin layer containing one or two resins selected from a modified olefin-based resin and a hydrogenated styrene-based thermoplastic elastomer between the uneven shape layer and the base layer. The liquid-repellent resin sheet according to the above. The convex shape includes a first convex shape and a second convex shape, wherein the height of the first convex shape and the height of the second convex shape are each 20 μm to 150 μm, The liquid-repellent resin sheet according to any one of claims 1 to 6 , wherein a vertex interval is 20 µm to 100 µm. The said 1st convex shape and the 2nd convex shape are staggered, The ratio of the height of a 2nd convex shape with respect to the height of a 1st convex shape is 0.4 or more and 0.8 or less. lyophobic resin sheet according to 7.   The liquid-repellent resin sheet according to any one of claims 1 to 8, wherein the hydrophobic oxide fine particles are hydrophobic silica fine particles having a trimethylsilyl group on the surface.   10. The liquid repellent layer according to claim 1, wherein the content of the hydrophobic oxide fine particles is 20 to 70% by mass, and the content of the fluorine-based copolymer resin is 70 to 30% by mass. 11. The liquid-repellent resin sheet according to any one of the preceding claims.   The liquid-repellent resin sheet according to any one of claims 1 to 10, wherein the thickness of the uneven shape layer is 50 µm to 200 µm. A molded article formed by heating and stretching the liquid-repellent resin sheet according to any one of claims 1 to 11 . 13. The molded article according to claim 12 , wherein a contact angle when the surface of the uneven layer contacts an oil-based liquid or a surfactant-based liquid is 120 ° or more, and a falling angle is 70 ° or less. For convex height of the liquid repellent resin sheet, reduction ratio of the convex height is less than 30%, the molded article according to claim 12 or 13. The molded product according to any one of claims 12 to 14 , wherein the molded product has a flange portion and a bottom portion, and a ratio of a thickness of the bottom portion to a thickness of the flange portion is 0.40 to 0.95. Goods. The molded article according to any one of claims 12 to 15 , which is a container for living goods. The molded article according to any one of claims 12 to 15 , which is a food container. Forming a concavo-convex layer having at least one or more convex shapes on one surface;
A step of cross-linking the polyolefin resin by irradiating the surface of the uneven layer with an electron beam, wherein the uneven layer is made of a resin composition containing a polyolefin resin;
On the surface having the convex shape of the concave-convex shape layer, it possesses a step of forming a liquid repellent layer containing a hydrophobic oxide fine particles and fluorine-based copolymer resin, the surface of the irregularities layer, A method for producing a liquid-repellent resin sheet, wherein a contact angle at the time of contact with an oil-based liquid or a surfactant-based liquid is 130 ° or more and a falling angle is 40 ° or less . Forming a concavo-convex layer having at least one or more convex shapes on one surface;
A step of cross-linking the polyolefin resin by irradiating the surface of the uneven layer with an electron beam, wherein the uneven layer is made of a resin composition containing a polyolefin resin;
On the surface having the convex shape of the concave-convex shape layer, and forming a liquid repellent layer containing a hydrophobic oxide fine particles and fluorine-based copolymer resin, a possess, at 230 ° C. of the polyolefin resin The method for producing a liquid-repellent resin sheet, wherein the melt mass flow rate is 5 g / 10 minutes or more .